Transformative Powder Fibration toward Hierarchical Ceramic Aerogels for Multifunctional Aerospace Systems

ABSTRACT Extreme aerospace environments demand ultralight materials capable of simultaneously withstanding rapid thermal fluctuations, intense mechanical shocks, and strong electromagnetic radiation. However, integrating thermal stability, mechanical resilience, and multifunctionality within a single ceramic aerogel remains challenging due to the intrinsic brittleness and structural instability of conventional systems. Here, we report a scalable powder‐to‐fiber transformation strategy to construct hierarchical ceramic aerogels reinforced with cellulose‐derived topological microscrolls. This process converts particle‐based networks into entangled fibrous frameworks, enabling cooperative deformation and structural robustness. As a result, the aerogels exhibit near‐temperature‐invariant superelasticity (up to 95% strain recovery), negative thermal expansion, and ultralow thermal conductivity (3.6 mW m − 1 K − 1 in vacuum). They maintain structural integrity under extreme conditions, including direct flame exposure and rapid thermal cycling from −196°C to 1300°C, while delivering high electromagnetic interference shielding effectiveness (above 56 dB across 8.2–40 GHz). These integrated properties establish a robust strategy for designing multifunctional ceramic aerogels for aerospace structures, thermal protection, and other extreme‐environment applications.